EP2031361A2 - Method for designating a component having a heat insulation layer and for determining its operating time - Google Patents

Method for designating a component having a heat insulation layer and for determining its operating time Download PDF

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EP2031361A2
EP2031361A2 EP08162572A EP08162572A EP2031361A2 EP 2031361 A2 EP2031361 A2 EP 2031361A2 EP 08162572 A EP08162572 A EP 08162572A EP 08162572 A EP08162572 A EP 08162572A EP 2031361 A2 EP2031361 A2 EP 2031361A2
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Prior art keywords
ysz
component
thermal barrier
doped
barrier coating
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German (de)
French (fr)
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EP2031361A3 (en
EP2031361B1 (en
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Hans-Peter Bossmann
Dietrich Eckardt
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General Electric Technology GmbH
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Alstom Technology AG
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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01K—MEASURING TEMPERATURE; MEASURING QUANTITY OF HEAT; THERMALLY-SENSITIVE ELEMENTS NOT OTHERWISE PROVIDED FOR
    • G01K3/00—Thermometers giving results other than momentary value of temperature
    • G01K3/02—Thermometers giving results other than momentary value of temperature giving means values; giving integrated values
    • G01K3/04—Thermometers giving results other than momentary value of temperature giving means values; giving integrated values in respect of time
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01K—MEASURING TEMPERATURE; MEASURING QUANTITY OF HEAT; THERMALLY-SENSITIVE ELEMENTS NOT OTHERWISE PROVIDED FOR
    • G01K11/00—Measuring temperature based upon physical or chemical changes not covered by groups G01K3/00, G01K5/00, G01K7/00 or G01K9/00
    • G01K11/30—Measuring temperature based upon physical or chemical changes not covered by groups G01K3/00, G01K5/00, G01K7/00 or G01K9/00 using measurement of the effect of a material on X-radiation, gamma radiation or particle radiation

Definitions

  • the reconditionability is determined by the component boundary conditions, such as operating time at high temperature, manufacturer of the coating and coating quality. Since usually commercially available YSZ (Yttria stabilized zirconia) is applied to the component surfaces to be coated using standard coating methods, components with renewed thermal barrier coatings generally do not allow any conclusions about the manufacturer of the coating, the relevant process parameters and the material quality. Experience has shown that even with the same starting material for the YSZ coating, significant differences in the lifetime of TBCs occur. If the boundary conditions specified by the coating and the operation of the component are not known, the risk of a misjudgment of the component state also increases.
  • YSZ Yttria stabilized zirconia
  • Dopants of YSZ coatings are known per se and are used for various purposes, such as an infiltration of Cr 2 O 3 as corrosion protection, or dopants with Sc 2 O 3 , Yb 2 O 3 , Nd 2 O 3 , Sm 2 O 3 , Gd 2 O 3 , NiO and Cr 2 O 3 for reducing the thermal conductivity of thermal barrier coatings.
  • DE-A-197 33 700 is a hard-reinforced ZrO 2 stabilized ceramics with mechanical stability under hydrothermal stress known.
  • the ZrO 2 ceramic contains not only a hard material component (eg TiC) Al 2 O 3 and the remainder a stabilized ZrO 2 phase with a solid solution of Y 2 O 3 and CeO 2 .
  • a Y 2 O 3 -containing ZrO 2 powder is provided with a cerium doping and then mixed with the hard material component and with Al 2 O 3 in a liquid mixture.
  • the YSZ ceramic layer is doped with a mixture of appropriately selected metal oxides for simultaneous marking of the component and determination of the operating time of the component at temperature.
  • the thermal barrier coating may be locally colored to visualize the identification of the device by doping with a suitable metal oxide.
  • a coloring metal oxide preferred for coloring is hematite (Fe 2 O 3 ). When using metal oxides without their own color, the marking is made visible with technical aids, eg IR light, UV light or X-ray diffraction.
  • the thermal barrier coating is doped overall, i.e., over the entire device surface, or at selected locations, such that, due to the duration of operation at high temperature, a faster or a slower change in the lattice parameters of the doped YSZ crystal phases occurs as compared to the undoped YSZ crystal phases.
  • the thermal barrier coating is preferably doped with at least one alkaline earth metal oxide, in particular with magnesium oxide (MgO) and / or calcium oxide (CaO).
  • the thermal barrier coating is preferably doped with at least one rare earth metal oxide, in particular with ytterbium oxide (Yb 2 O 3 ) and / or gadolinium oxide (Gd 2 O 3 ).
  • the sum of the concentrations of all dopants is preferably 0.0001 to 5 wt .-%, in particular 0.01 to 2 wt .-%.
  • the dopants can be localized and patterned, eg. to identify a specific manufacturer of the thermal barrier coating in the form of a logo.
  • the doping with high-temperature-stable metal oxides leads to no change in the change of the lattice parameters compared to the undoped YSZ crystal phases.
  • the lattice parameters of the high temperature stable metal oxides are characteristic of the operating life at the temperature of the device.
  • the mixing ratio of the dopants in the YSZ crystal phases changes in a characteristic manner for the component. Since the high-temperature-stable metal oxides used for the doping can be distinguished well from the deposits customary in gas turbines, metallographic analysis methods, such as X-ray diffraction or emission spectroscopy, which are determined due to the duration of operation at temperature time-varying mixing ratio, which allows a conclusion on the operating life of the component at temperature.
  • a component 10 for example a turbine blade
  • M Fe, Co, Ni
  • the adhesion promoter layer 14 serves primarily to protect the oxidation of the substrate 12 and the better adhesion of a, for example, as thermal barrier coating 16 by plasma spraying applied to the substrate 12, with metal oxides or with a high-melting, oxidation-resistant metal doped YSZ ceramic layer.
  • an aluminide layer as adhesion promoter layer be used. This can be generated by aluminum diffusion into the substrate surface.
  • Fig. 2 shows an X-ray diffraction spectrum of the lattice parameters of the t, t 'and c phases of YSZ after different operating times at a temperature of 1300 ° C.
  • Clearly recognizable is the time of operation at the temperature of 1300 ° C dependent temporal change of the lattice parameters.
  • a doping of YSZ with CaO or MgO leads to a faster, a doping with Yb 2 O 3 or Gd 2 O 3 to a slower change in the lattice parameters compared to undoped YSZ (not shown in the drawing).
  • Figure 3 1 shows a surface of a coating of undoped YSZ as a bright surface 18 with a small section of a dark surface 20.
  • the dark surface 20 was formed by doping YSZ by infiltration of a mixture of CaO, MgAl 2 O 4 (spinel) and Fe 2 O 3 ( hematite).
  • the dark area 20 corresponds to a brownish discoloration caused by hematite.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
  • Turbine Rotor Nozzle Sealing (AREA)
  • Coating By Spraying Or Casting (AREA)
  • Investigating Or Analyzing Materials Using Thermal Means (AREA)

Abstract

To determine the working life or working temperature of a component (10), e.g. a turbine vane, with a thermal insulation layer (16) of a material (YSZ) composed of zirconium oxide (ZrO 2) stabilized with Yttrium oxide (Y 2O 3), the surface is visibly marked with at least one metal oxide. The surface of the YSZ material is observed at a temperature with a rapid or slow alteration of the YSZ grid parameters in the marked and unmarked zones for comparison with a calibration curve.

Description

TECHNISCHES GEBIETTECHNICAL AREA

Die Erfindung betrifft ein Verfahren zur Kennzeichnung und zur Bestimmung der Betriebsdauer oder Betriebstemperatur eines mit einer Wärmedämmschicht aus mit Yttriumoxid (Y2O3) stabilisiertem Zirkondioxid (ZrO2) [YSZ] beschichteten Bauteils.The invention relates to a method for identifying and determining the operating time or operating temperature of a component coated with a yttria (Y 2 O 3 ) stabilized zirconia (ZrO 2 ) [YSZ] thermal barrier coating.

STAND DER TECHNIKSTATE OF THE ART

In stationären Gasturbinen und in Gasturbinen von Flugzeugmotoren werden mit einer Wärmedämmschicht oder TBC (thermal barrier coating) beschichtete Bauteile eingesetzt. Derartige Bauteile werden meist von innen oder von einer Seite gekühlt und sind auf der heissen Seite mit der keramischen TBC-Schicht wärmeisoliert. Eine niedrige Wärmeleitfähigkeit ist bezüglich der erforderlichen Kühlluft und Dicke der TBC-Schicht vorteilhaft. Die keramische TBC-Schicht besteht beispielsweise aus mit Yttriumoxid stabilisiertem Zirkondioxid (YSZ) oder aus anderen keramischen Materialien und Stabilisatoren und kann mit verschiedenen Verfahren, wie z.B. Air Plasma Spray (APS), Electron Beam Physical Vapor Deposition (EB-PVD) usw., mit oder ohne Haftvermittlerschicht auf die Oberfläche von metallischen Substraten appliziert werden.In stationary gas turbines and in gas turbines of aircraft engines coated components are used with a thermal barrier coating or TBC (thermal barrier coating). Such components are usually cooled from the inside or from one side and are thermally insulated on the hot side with the ceramic TBC layer. A low thermal conductivity is advantageous in terms of the required cooling air and thickness of the TBC layer. The ceramic TBC layer consists, for example, of yttria-stabilized zirconia (YSZ) or others ceramic materials and stabilizers and can be applied to the surface of metallic substrates by various methods, such as Air Plasma Spray (APS), Electron Beam Physical Vapor Deposition (EB-PVD), etc., with or without a primer layer.

Bauteile von Gasturbinen sind oft extreme zyklischen Temperaturwechselbeanspruchungen ausgesetzt. Beim Aufheizen und Abkühlen der Bauteile entstehen aufgrund unterschiedlicher thermischen Ausdehnungskoeffizienten der verschiedenen Werkstoffe thermische Spannungen, die zur Schädigung und zum Versagen des Gefüges führen können. Im Betrieb altern die Bauteile abhängig von der Temperaturbelastung des Bauteils und werden nach einer gewissen Betriebsdauer bei Temperatur rekonditioniert oder verschrottet. Beim Rekonditionieren werden typischerweise die TBC-Beschichtung und eine gegebenenfalls vorhandene Haftvermittlerschicht entfernt. Anschliessend wird das Bauteil nach weiteren Arbeitsschritten, wie Vorbehandlung des Metallsubstrats und Aufbringen einer neuen Haftvermittlerschicht (bond coat), wieder mit einer neuen Wärmedämmschicht beschichtet und eingesetzt.Components of gas turbines are often exposed to extreme cyclic thermal cycling. During heating and cooling of the components thermal stresses occur due to different thermal expansion coefficients of the different materials, which can lead to damage and failure of the microstructure. During operation, the components age depending on the temperature load of the component and are reconditioned or scrapped at temperature after a certain period of operation. During reconditioning, typically the TBC coating and an optional primer layer are removed. Subsequently, after further work steps, such as pretreatment of the metal substrate and application of a new adhesion promoter layer (bond coat), the component is again coated and used with a new thermal barrier coating.

Die Rekonditionierbarkeit wird durch die Bauteilrandbedingungen, wie z.B. Betriebsdauer bei Hochtemperatur, Hersteller der Beschichtung und Beschichtungsqualität, bestimmt. Da üblicherweise kommerziell verfügbares YSZ (Yttria stabilized Zirconia) unter Anwendung von Standardbeschichtungsverfahren auf die zu beschichtenden Bauteiloberflächen appliziert wird, lassen Bauteile mit erneuerten Wärmedämmschichten im allgemeinen keinen Rückschluss auf den Hersteller der Beschichtung, die relevanten Prozessparameter und die Materialqualität zu. Die Erfahrung zeigt, dass selbst bei gleichem Ausgangsmaterial für die YSZ-Beschichtung erhebliche Unterschiede bezüglich der Lebensdauer von TBCs auftreten. Sind die durch die Beschichtung und den Betrieb des Bauteils vorgegebenen Randbedingungen nicht bekannt, erhöht sich zudem das Risiko einer Fehlbeurteilung des Bauteilzustandes.The reconditionability is determined by the component boundary conditions, such as operating time at high temperature, manufacturer of the coating and coating quality. Since usually commercially available YSZ (Yttria stabilized zirconia) is applied to the component surfaces to be coated using standard coating methods, components with renewed thermal barrier coatings generally do not allow any conclusions about the manufacturer of the coating, the relevant process parameters and the material quality. Experience has shown that even with the same starting material for the YSZ coating, significant differences in the lifetime of TBCs occur. If the boundary conditions specified by the coating and the operation of the component are not known, the risk of a misjudgment of the component state also increases.

Dotierungen von YSZ-Beschichtungen sind an sich bekannt und werden für verschiedene Zwecke eingesetzt, so z.B. eine Infiltration von Cr2O3 als Korrosionsschutz, oder Dotierungen mit Sc2O3, Yb2O3, Nd2O3, Sm2O3, Gd2O3, NiO und Cr2O3 zur Reduzierung der Wärmeleitfähigkeit von Wärmedämmschichten.Dopants of YSZ coatings are known per se and are used for various purposes, such as an infiltration of Cr 2 O 3 as corrosion protection, or dopants with Sc 2 O 3 , Yb 2 O 3 , Nd 2 O 3 , Sm 2 O 3 , Gd 2 O 3 , NiO and Cr 2 O 3 for reducing the thermal conductivity of thermal barrier coatings.

Aus DE-A-197 33 700 ist eine hartstoffverstärkte stabilisierte ZrO2-Keramik mit mechanischer Stabilität unter hydrothermaler Beanspruchung bekannt. Die ZrO2-Keramik enthält neben einer Hartstoffkomponente (z.B. TiC) Al2O3 und als Rest eine stabilisierte ZrO2 -Phase mit einer festen Lösung von Y2O3 und CeO2. Zur Herstellung der ZrO2-Keramik wird ein Y2O3 enthaltendes ZrO2-Pulver mit einer Cer-Dotierung versehen und dann mit der Hartstoffkomponente und mit Al2O3 gemeinsam in einer Flüssigkeit mischgemahlen.Out DE-A-197 33 700 is a hard-reinforced ZrO 2 stabilized ceramics with mechanical stability under hydrothermal stress known. The ZrO 2 ceramic contains not only a hard material component (eg TiC) Al 2 O 3 and the remainder a stabilized ZrO 2 phase with a solid solution of Y 2 O 3 and CeO 2 . To produce the ZrO 2 ceramic, a Y 2 O 3 -containing ZrO 2 powder is provided with a cerium doping and then mixed with the hard material component and with Al 2 O 3 in a liquid mixture.

DARSTELLUNG DER ERFINDUNGPRESENTATION OF THE INVENTION

Der Erfindung liegt die Aufgabe zugrunde, ein Verfahren der eingangs genannten Art anzugeben, welches eine einfache Identifizierung des Herstellers der Beschichtung ermöglicht und mit dem gleichzeitig die Betriebsdauer der beschichteten Bauteile bei Hochtemperatur zuverlässig bestimmt werden kann. Mit einer Wärmedämmschicht beschichtete Bauteile für Hochtemperaturanwendungen sind insbesondere in stationären Gasturbinen und in Gasturbinen von Flugzeugmotoren eingesetzte Bauteile, wie z.B. Leit- oder Laufschaufeln oder Liner in einer Brennkammer.The invention has for its object to provide a method of the type mentioned, which allows easy identification of the manufacturer of the coating and with the same time the service life of the coated components can be reliably determined at high temperature. Thermal barrier coating coated components for high temperature applications are especially components used in stationary gas turbines and in gas turbines of aircraft engines, such as e.g. Guiding or moving blades or liners in a combustion chamber.

Zur erfindungsgemässen Lösung der Aufgabe führt, dass die Wärmedämmschicht in wenigstens einem Oberflächenbereich des Bauteils zur Markierung mit wenigstens einem Metalloxid dotiert wird, wobei das Metalloxid so ausgewählt wird, dass der dotierte Bereich von YSZ

  • zur Kennzeichnung des Bauteils sichtbar ist oder mit optischen Mitteln sichtbar gemacht werden kann, und
  • zur Bestimmung der Betriebsdauer des Bauteils bei Temperatur eine langsamere oder schnellere Änderung der Gitterparameter von YSZ im Vergleich zu undotiertem YSZ bewirkt und die Betriebsdauer bei Temperatur durch Vergleich der Gitterparameter mit einer bekannten Kalibrierkennlinie bestimmt wird.
To achieve the object according to the invention, the heat-insulating layer is doped in at least one surface region of the component for marking with at least one metal oxide, the metal oxide being selected such that the doped region of YSZ
  • is visible for identification of the component or can be visualized by optical means, and
  • to determine the operating time of the component at temperature, a slower or faster change of the lattice parameters of YSZ compared to undoped YSZ causes and the operating time is determined at temperature by comparing the lattice parameters with a known calibration curve.

Bei einer bevorzugten Ausführung des erfindungsgemässen Verfahrens wird die YSZ-Keramikschicht zur gleichzeitigen Kennzeichnung des Bauteils und Bestimmung der Betriebsdauer des Bauteils bei Temperatur mit einer Mischung von entsprechend ausgewählten Metalloxiden dotiert.In a preferred embodiment of the method according to the invention, the YSZ ceramic layer is doped with a mixture of appropriately selected metal oxides for simultaneous marking of the component and determination of the operating time of the component at temperature.

Die Wärmedämmschicht kann zum Sichtbarmachen der Kennzeichnung des Bauteils durch Dotierung mit einem geeigneten Metalloxid lokal gefärbt sein. Ein zur Färbung bevorzugtes färbende Metalloxid ist Hämatit (Fe2O3) ist. Bei Verwendung von Metalloxiden ohne Eigenfarbe erfolgt das Sichtbarmachen der Kennzeichnung mit technischen Hilfsmitteln, z.B. IR-Licht, UV-Licht oder Röntgenbeugung.The thermal barrier coating may be locally colored to visualize the identification of the device by doping with a suitable metal oxide. A coloring metal oxide preferred for coloring is hematite (Fe 2 O 3 ). When using metal oxides without their own color, the marking is made visible with technical aids, eg IR light, UV light or X-ray diffraction.

Abhängig von der Höhe der Betriebstemperatur und den zu erwartenden Betriebszeiten kann es vorteilhaft sein, die Änderungen der Gitterparameter des dotierten YSZ entsprechend anzupassen. Die Wärmedämmschicht wird insgesamt, d.h., über die gesamte Bauteiloberfläche, oder an ausgewählten Stellen derart dotiert, dass aufgrund der Betriebsdauer bei Hochtemperatur eine schnellere oder eine langsamere Änderung der Gitterparameter der dotierten YSZ-Kristallphasen im Vergleich zu den undotierten YSZ-Kristallphasen eintritt.Depending on the level of the operating temperature and the expected operating times, it may be advantageous to adapt the changes in the grating parameters of the doped YSZ accordingly. The thermal barrier coating is doped overall, i.e., over the entire device surface, or at selected locations, such that, due to the duration of operation at high temperature, a faster or a slower change in the lattice parameters of the doped YSZ crystal phases occurs as compared to the undoped YSZ crystal phases.

Zur schnelleren Änderung der Gitterparameter des dotierten YSZ im Vergleich zu undotiertem YSZ wird die Wärmedämmschicht bevorzugt mit wenigstens einem Erdalkalimetalloxid, insbesondere mit Magnesiumoxid (MgO) und/oder Kalziumoxid (CaO), dotiert.For faster modification of the lattice parameters of the doped YSZ compared to undoped YSZ, the thermal barrier coating is preferably doped with at least one alkaline earth metal oxide, in particular with magnesium oxide (MgO) and / or calcium oxide (CaO).

Zur langsameren Änderung der Gitterparameter des dotierten YSZ im Vergleich zu undotiertem YSZ wird die Wärmedämmschicht bevorzugt mit wenigstens einem Seltenerdmetalloxid, insbesondere mit Ytterbiumoxid (Yb2O3) und/oder Gadoliniumoxid (Gd2O3), dotiert.For a slower change in the lattice parameters of the doped YSZ in comparison to undoped YSZ, the thermal barrier coating is preferably doped with at least one rare earth metal oxide, in particular with ytterbium oxide (Yb 2 O 3 ) and / or gadolinium oxide (Gd 2 O 3 ).

Zur Charakterisierung des Bauteil ohne Änderung der Gitterparameter von YSZ im Vergleich zu undotiertem YSZ wird die Wärmedämmschicht mit wenigstens einem hochtemperaturstabilen Metalloxid, insbesondere mit einem oder mehreren Metalloxiden ausgewählt aus der Gruppe bestehend aus Fe2O3, Cr2O3, Al2O3, NiO und CoO, dotiert. Zusätzlich kann die Wärmedämmschicht mit einem hochschmelzenden, oxidationsbeständigen Metall, insbesondere mit Platin (Pt) und/oder Rhenium (Re), dotiert werden.To characterize the component without changing the lattice parameters of YSZ compared to undoped YSZ, the thermal barrier coating with at least one high temperature stable metal oxide, in particular with one or more metal oxides selected from the group consisting of Fe 2 O 3 , Cr 2 O 3 , Al 2 O 3 , NiO and CoO, doped. In addition, the heat-insulating layer can be doped with a high-melting, oxidation-resistant metal, in particular with platinum (Pt) and / or rhenium (Re).

Die Summe der Konzentrationen aller Dotierungen beträgt bevorzugt 0,0001 bis 5 Gew.-%, insbesondere 0,01 bis 2 Gew.-%.The sum of the concentrations of all dopants is preferably 0.0001 to 5 wt .-%, in particular 0.01 to 2 wt .-%.

Die Dotierungen können lokal begrenzt und als Musters, zB. zur Kennzeichnung eines bestimmten Herstellers der Wärmedämmschicht in Form eines Logos, ausgeführt sein.The dopants can be localized and patterned, eg. to identify a specific manufacturer of the thermal barrier coating in the form of a logo.

Die Dotierungen können dem Ausgangsmaterial für die Wärmedämmschicht zugesetzt werden, durch Infiltration erfolgen oder durch eine Umwandlungsreaktion innerhalb der Wärmedämmschicht erzeugt werden.The dopants can be added to the starting material for the thermal barrier coating, be made by infiltration or generated by a conversion reaction within the thermal barrier coating.

Die Dotierung mit hochtemperaturstabilen Metalloxiden führt zu keiner Veränderung der Änderung der Gitterparameter gegenüber den undotierten YSZ-Kristallphasen. Die Gitterparameter der hochtemperaturstabilen Metalloxide sind jedoch charakteristisch für die Betriebsdauer bei Temperatur des Bauteils. ändert sich jedoch das Mischungsverhältnis der Dotierungen in der YSZ-Kristallphasen in einer für das Bauteil charakteristischen Weise. Da die für die Dotierungen verwendeten hochtemperaturstabilen Metalloxide sich von den in Gasturbinen üblichen Ablagerungen gut unterscheiden lassen, kann mit metallographischen Analyseverfahren, wie z.B. Röntgenbeugung oder Emissionsspektroskopie, das aufgrund der Betriebsdauer bei Temperatur sich zeitlich ändernde Mischungsverhältnis bestimmt werden, was einen Rückschluss auf die Betriebsdauer des Bauteils bei Temperatur zulässt.The doping with high-temperature-stable metal oxides leads to no change in the change of the lattice parameters compared to the undoped YSZ crystal phases. However, the lattice parameters of the high temperature stable metal oxides are characteristic of the operating life at the temperature of the device. However, the mixing ratio of the dopants in the YSZ crystal phases changes in a characteristic manner for the component. Since the high-temperature-stable metal oxides used for the doping can be distinguished well from the deposits customary in gas turbines, metallographic analysis methods, such as X-ray diffraction or emission spectroscopy, which are determined due to the duration of operation at temperature time-varying mixing ratio, which allows a conclusion on the operating life of the component at temperature.

KURZE ERLÄUTERUNG DER FIGURENBRIEF EXPLANATION OF THE FIGURES

Weitere Vorteile Merkmale und Einzelheiten der Erfindung ergeben sich aus der nachfolgenden Beschreibung bevorzugter Ausführungsbeispiele sowie anhand der Zeichnung; diese in

Fig. 1
einen Querschnitt durch eine Beschichtung eines thermisch bean-spruchten Bauteils;
Fig. 2
ein Röntgenbeugungsspektrum der Gitterparameter von YSZ nach unterschiedlichen Zeiten bei einer Temperatur von 1300 °C;
Fig. 3
eine Draufsicht auf die Oberfläche einer YSZ-Beschichtung mit einem dotierten Bereich.
Further advantages Features and details of the invention will become apparent from the following description of preferred embodiments and from the drawing; this in
Fig. 1
a cross section through a coating of a thermally stressed component;
Fig. 2
an X-ray diffraction spectrum of the lattice parameters of YSZ after different times at a temperature of 1300 ° C;
Fig. 3
a plan view of the surface of a YSZ coating with a doped region.

WEGE ZUR AUSFÜHRUNG DER ERFINDUNGWAYS FOR CARRYING OUT THE INVENTION

In Fig. 1 ist der Aufbau eines Bauteils 10, z.B. einer Turbinenschaufel, beispielhaft wiedergegeben. Auf einem Substrat 12 aus einer Superlegierung auf Nickelbasis ist eine Haftvermittlerschicht 14 aus einer MCrAIY-Legierung (M = Fe, Co, Ni) aufgebracht. Die Haftvermittlerschicht 14 dient hauptsächlich dem Oxidationsschutz des Substrats 12 sowie der besseren Haftung einer beispielsweise als Wärmedämmschicht 16 durch Plasmaspritzen auf das Substrat 12 aufgetragenen, mit Metalloxiden oder mit einem hochschmelzenden, oxidationsbeständigen Metall dotierten YSZ-Keramikschicht. Alternativ kann auch eine Aluminidschicht als Haftvermittlerschicht verwendet werden. Diese kann durch Aluminiumdiffusion in die Substratoberfläche erzeugt werden.In Fig. 1 the structure of a component 10, for example a turbine blade, is reproduced by way of example. On a nickel base superalloy substrate 12, an adhesion promoter layer 14 of an MCrAlY alloy (M = Fe, Co, Ni) is deposited. The adhesion promoter layer 14 serves primarily to protect the oxidation of the substrate 12 and the better adhesion of a, for example, as thermal barrier coating 16 by plasma spraying applied to the substrate 12, with metal oxides or with a high-melting, oxidation-resistant metal doped YSZ ceramic layer. Alternatively, it is also possible to use an aluminide layer as adhesion promoter layer be used. This can be generated by aluminum diffusion into the substrate surface.

Fig. 2 zeigt ein Röntgenbeugungsspektrum der Gitterparameter der t-, t'- und c-Phasen von YSZ nach verschiedenen Betriebszeiten bei einer Temperatur von 1300 °C. Deutlich erkennbar ist die von der Betriebsdauer bei der Temperatur von 1300 °C abhängige zeitliche Änderung der Gitterparameter. Eine Dotierung von YSZ mit CaO oder MgO führen zu einer schnelleren, eine Dotierung mit Yb2O3 oder Gd2O3 zu einer langsameren Veränderung der Gitterparameter im Vergleich zu undotiertem YSZ (in der Zeichnung nicht dargestellt). Fig. 2 shows an X-ray diffraction spectrum of the lattice parameters of the t, t 'and c phases of YSZ after different operating times at a temperature of 1300 ° C. Clearly recognizable is the time of operation at the temperature of 1300 ° C dependent temporal change of the lattice parameters. A doping of YSZ with CaO or MgO leads to a faster, a doping with Yb 2 O 3 or Gd 2 O 3 to a slower change in the lattice parameters compared to undoped YSZ (not shown in the drawing).

Fig.3 zeigt eine Oberfläche einer Beschichtung aus undotiertem YSZ als helle Fläche 18 mit einem kleinen Ausschnitt einer dunklen Fläche 20. Die dunkle Fläche 20 entstand durch Dotieren von YSZ durch Infiltration eines Gemisches von CaO, MgAl2O4 (Spinell) und Fe2O3 (Hämatit). Die dunkle Fläche 20 entspricht einer durch Hämatit hervorgerufenen, bräunlichen Verfärbung. Figure 3 1 shows a surface of a coating of undoped YSZ as a bright surface 18 with a small section of a dark surface 20. The dark surface 20 was formed by doping YSZ by infiltration of a mixture of CaO, MgAl 2 O 4 (spinel) and Fe 2 O 3 ( hematite). The dark area 20 corresponds to a brownish discoloration caused by hematite.

BEZUGSZEICHENLISTELIST OF REFERENCE NUMBERS

1010
Bauteilcomponent
1212
Substratsubstratum
1414
HaftvermittlerschichtBonding layer
1616
Wärmedämmschichtthermal barrier
1818
Oberfläche einer YSZ-BeschichtungSurface of a YSZ coating
2020
dotierter Ausschnitt aus 18endowed section from 18

Claims (12)

Verfahren zur Kennzeichnung und zur Bestimmung der Betriebsdauer oder Betriebstemperatur eines mit einer Wärmedämmschicht (16) aus mit Yttriumoxid (Y2O3) stabilisiertem Zirkondioxid (ZrO2) [YSZ] beschichteten Bauteils (10),
dadurch gekennzeichnet, dass
die Wärmedämmschicht (16) in wenigstens einem Oberflächenbereich des Bauteils (10) zur Markierung mit wenigstens einem Metalloxid dotiert wird, wobei das Metalloxid so ausgewählt wird, dass der dotierte Bereich von YSZ - zur Kennzeichnung des Bauteils (10) sichtbar ist oder mit optischen Mitteln sichtbar gemacht werden kann, und - zur Bestimmung der Betriebsdauer des Bauteils (10) bei Temperatur eine langsamere oder schnellere Änderung der Gitterparameter von YSZ im Vergleich zu undotiertem YSZ bewirkt und die Betriebsdauer bei Temperatur durch Vergleich der Gitterparameter mit einer bekannten Kalibrierkennlinie bestimmt wird. Method for identifying and determining the operating time or operating temperature of a zirconia (ZrO 2 ) [YSZ] coated component (10) stabilized with a yttria (Y 2 O 3 ) thermal barrier coating (16),
characterized in that
the heat-insulating layer (16) is doped in at least one surface region of the component (10) for marking with at least one metal oxide, wherein the metal oxide is selected such that the doped region of YSZ - is visible for identification of the component (10) or can be made visible by optical means, and - For determining the operating time of the component (10) at temperature a slower or faster change of the lattice parameters of YSZ compared to undoped YSZ causes and the operating time is determined by comparing the lattice parameters with a known calibration characteristic at temperature. Verfahren nach Anspruch 1, dadurch gekennzeichnet, dass die Wärmedämmschicht (16) zum Sichtbarmachen der Kennzeichnung des Bauteils (10) durch Dotierung mit einem geeigneten Metalloxid lokal gefärbt wird.A method according to claim 1, characterized in that the thermal barrier coating (16) for visualizing the marking of the component (10) is locally colored by doping with a suitable metal oxide. Verfahren nach Anspruch 2, dadurch gekennzeichnet, dass das färbende Metalloxid Hämatit (Fe2O3) ist.A method according to claim 2, characterized in that the coloring metal oxide is hematite (Fe 2 O 3 ). Verfahren nach Anspruch 1, dadurch gekennzeichnet, dass die Wärmedämmschicht (16) zur schnelleren Änderung der Gitterparameter des dotierten YSZ im Vergleich zu undotiertem YSZ mit wenigstens einem Erdalkalimetalloxid, insbesondere mit Magnesiumoxid (MgO) und/oder Kalziumoxid (CaO), dotiert wird.A method according to claim 1, characterized in that the thermal barrier coating (16) for faster change of the lattice parameters of the doped YSZ compared to undoped YSZ with at least one alkaline earth metal oxide, in particular with magnesium oxide (MgO) and / or calcium oxide (CaO). Verfahren nach Anspruch 1, dadurch gekennzeichnet, dass die Wärmedämmschicht (10) zur langsameren Änderung der Gitterparameter des dotierten YSZ im Vergleich zu undotiertem YSZ mit wenigstens einem Seltenerdmetalloxid, insbesondere mit Ytterbiumoxid (Yb2O3) und/oder Gadoliniumoxid (Gd2O3), dotiert wird.A method according to claim 1, characterized in that the thermal barrier coating (10) for slower change of the lattice parameters of the doped YSZ compared to undoped YSZ with at least one rare earth metal oxide, in particular with ytterbium oxide (Yb 2 O 3 ) and / or gadolinium oxide (Gd 2 O 3 ), is doped. Verfahren nach Anspruch 1, dadurch gekennzeichnet, dass die Wärmedämmschicht (10) zur Charakterisierung des Bauteils (10) ohne Änderung der Gitterparameter von YSZ im Vergleich zu undotiertem YSZ mit wenigstens einem hochtemperaturstabilen Metalloxid, insbesondere mit einem oder mehreren Metalloxiden ausgewählt aus der Gruppe bestehend aus Fe2O3, Cr2O3, Al2O3, NiO und CoO, dotiert wird.A method according to claim 1, characterized in that the thermal barrier coating (10) for characterizing the component (10) without changing the lattice parameters of YSZ compared to undoped YSZ with at least one high temperature stable metal oxide, in particular with one or more metal oxides selected from the group consisting of Fe 2 O 3 , Cr 2 O 3 , Al 2 O 3 , NiO and CoO is doped. Verfahren nach Anspruch 6, dadurch gekennzeichnet, dass die Wärmedämmschicht (10) zusätzlich mit einem hochschmelzenden, oxidationsbeständigen Metall, insbesondere mit Platin (Pt) und/oder Rhenium (Re), dotiert wird.A method according to claim 6, characterized in that the heat-insulating layer (10) is additionally doped with a refractory, oxidation-resistant metal, in particular with platinum (Pt) and / or rhenium (Re). Verfahren nach einem der Ansprüche 1 bis 7, dadurch gekennzeichnet, dass die Summe der Konzentrationen aller Dotierungen 0,0001 bis 5 Gew. -%, insbesondere 0,01 bis 2 Gew. -%, beträgt.Method according to one of claims 1 to 7, characterized in that the sum of the concentrations of all dopants from 0.0001 to 5 wt -.%, In particular 0.01 to 2 wt -.% Is. Verfahren nach einem der Ansprüche 1 bis 8, dadurch gekennzeichnet, dass die Dotierungen lokal begrenzt und als Muster ausgeführt sind.Method according to one of claims 1 to 8, characterized in that the dopants are locally limited and designed as a pattern. Verfahren nach einem der Ansprüche 1 bis 9, dadurch gekennzeichnet, dass die Dotierungen dem Ausgangsmaterial für die Wärmedämmschicht (16) zugesetzt werden.Method according to one of claims 1 to 9, characterized in that the dopants are added to the starting material for the thermal barrier coating (16). Verfahren nach einem der Ansprüche 1 bis 9, dadurch gekennzeichnet, dass die Dotierungen durch Infiltration erfolgen.Method according to one of claims 1 to 9, characterized in that the doping takes place by infiltration. Verfahren nach einem der Ansprüche 1 bis 9, dadurch gekennzeichnet, dass die Dotierungen durch eine Umwandlungsreaktion innerhalb der Wärmedämmschicht (16) erzeugt werden.Method according to one of claims 1 to 9, characterized in that the dopants are generated by a conversion reaction within the thermal barrier coating (16).
EP08162572.5A 2007-08-31 2008-08-19 Method for designating a component having a heat insulation layer and for determining its operating time Active EP2031361B1 (en)

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US8252601B2 (en) 2012-08-28

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